CN101091003B - Method for forming tantalum nitride film - Google Patents

Method for forming tantalum nitride film Download PDF

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CN101091003B
CN101091003B CN2006800014652A CN200680001465A CN101091003B CN 101091003 B CN101091003 B CN 101091003B CN 2006800014652 A CN2006800014652 A CN 2006800014652A CN 200680001465 A CN200680001465 A CN 200680001465A CN 101091003 B CN101091003 B CN 101091003B
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gas
free radical
film
tantalum
formation method
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CN101091003A (en
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五户成史
丰田聪
牛川治宪
近藤智保
中村久三
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Ulvac Inc
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Ulvac Inc
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Abstract

A Ta-rich tantalum nitride film is formed as follows: a raw material gas composed of a coordinate compound wherein an N=(R,R') group (where R and R' may be the same as or different from each other and respectively represent an alkyl group having 1-6 carbon atoms) is coordinated to a Ta element is introduced into a vacuum chamber and adsorbed on a substrate; next an NH<SUB>3</SUB> gas is introduced therein; and then H radicals generated by activating a reaction gas are introduced therein for cutting and removing the R(R') group bonded to N. Consequently, a low-resistance tantalum nitride film having low C and N contents, high Ta/N ratio and secure adhesion to a Cu film can be obtained, and this tantalum nitride film is useful as a barrier film. By implanting tantalum particles into the thus-obtained film by sputtering, there can be obtained a still tantalum-richer film.

Description

The formation method of TaN film
Technical field
The present invention relates to the formation method of TaN film, particularly relate to according to ALD method (Atomic Layer6 Deposition: the atomic shell vapour deposition method) form the method for the useful TaN film of the barrier film used as wiring film.
Background technology
In recent years, the requirement of the microfabrication in the thin film fabrication technology of semiconductor applications is accelerated, followed it that various problems have taken place.
As being processed as example with the film distribution in the semiconducter device, as wiring material, owing to reasons such as resistivity are little, main flow is to use copper.But,, produce the low problem of reliability of device because copper has the etching difficulty, the character of easy diffusion in the insulating film of stratum basale.
In order to address this problem, in the past, by formation metallic films such as usefulness CVD methods on the inner wall surface of connecting hole between the multilayer in multilayered wiring structure (promptly, the blocking layer of electroconductibility), form the copper film thereon as wiring layer, make the insulating films such as silicon oxide layer of copper film and stratum basale directly not contact, prevent the diffusion of copper.
In this occasion, follow the miniaturization of above-mentioned multilayer wiredization and pattern, require profundity to be covered (step coverage) than ladders such as high fine contact hole and grooves and bury underground well with thin barrier film.
Therefore, for example, by repeating after making the substrate of moving in the vacuum tank be warming up to specified temperature, nitrogenous gas and a kind of gas that contains in the high melting point metal compound gas are being imported, after making it be adsorbed on the substrate, with the vacuum exhaust of this kind gas, then another kind of gas is imported, make it after reaction on the substrate, operation with this another kind gas vacuum exhaust, use forms the barrier film (for example, with reference to patent documentation 1) of desired thickness with the ALD method of atomic shell unit's degree laminated metal nitride film on substrate.
In addition, the also known ALD method etc. of using is piled up material layers such as Ta, TiN, TaN and is formed barrier film (for example, with reference to patent documentation 2).
Above-mentioned ALD method is similar with the CVD method on this aspect of chemical reaction that utilizes between precursor.But, in the common CVD method, utilize the precursor of gaseous phase to contact with each other the phenomenon that induces reaction, in contrast to this, in the ALD method, be different utilizing on two surface reaction this point between precursor.That is, be, by (for example making a kind of precursor if according to the ALD method, unstripped gas) under the state that is adsorbed on the substrate surface, supply with other precursor (for example, reactant gases), make two kinds of precursors contact with each other reaction, form desirable metallic membrane at substrate surface.In this occasion, being reflected on the substrate surface between the precursor of initial precursor that adsorbs and then supply on the substrate surface takes place with very fast speed.As precursor, can use any of solid, liquid, gaseous phase, unstripped gas is supported on N 2, supply with in such carrier gas such as Ar.This ALD method, as described above, be that the absorption process of unstripped gas and the unstripped gas of absorption and the reaction process of reactant gases alternately repeat, with the film forming method of atomic shell unit, because absorption/reaction is carried out in the apparent motion zone always, so have extraordinary step coverage, in addition, because unstripped gas and reactant gases are to supply respectively to react, so can improve film density etc., by these reasons, the ALD method receives publicity in recent years.
The atomic shell evaporation coating device in the past (ALD device) that carries out film formation according to above-mentioned ALD method is made of the film deposition system that is provided with vacuum-pumping equipment, in device, when being provided with substrate platform with heating installation, in the direction relative, dispose the gas introducing equipment in the courtyard portion of film deposition system with the substrate platform.As this ALD device, for example, known is that determined unstripped gas and reactant gases are caused in the time difference ground gatherer by the gas introducing equipment, repeat the absorption process of unstripped gas and auxiliary on one side with plasma body, the reaction process of one side and reactant gases reaction, with the such device (for example, with reference to patent documentation 3) that constitutes of the film that obtains the regulation thickness.
Patent documentation 1: the spy opens flat 11-54459 communique (claim 1 etc.)
Patent documentation 2: the spy opens 2004-6856 communique (claims etc.)
Patent documentation 3: the spy opens 2003-318174 communique (claims etc.)
Summary of the invention
In the occasion of above-mentioned prior art, use and contain the occasion of the organometallic compound gas of tantalum as unstripped gas, the content height of the C in the TaN film that obtains, N, in addition, the Ta/N ratio of components is low.Therefore, though guaranteed and the adaptation of Cu wiring film, there is the problem that is difficult to form as useful low-resistance tantalum nitride (TaN) film of barrier film.In order to address this problem, be necessary to develop the cut-out of the organic radicals such as alkyl in the unstripped gas is removed, reduce C content, and, the key that cuts off Ta and N, the possible film-forming process of raising Ta/N ratio of components.
Therefore, problem of the present invention is to solve above-mentioned prior art problems, provide and form that C, N content are low, Ta/N ratio of components height and as guaranteeing and the method for the low resistance TaN film that the barrier film of the adaptation of wiring film (for example, Cu wiring film) is useful.
The formation method of TaN film of the present invention, it is characterized in that, in vacuum chamber, importing has contained in the coordination on every side of tantalum element (Ta) N=(R, R ') (alkyl of R and R ' expression carbonatoms 1-6, can be identical group separately, also can be different groups) unstripped gas, the NH of title complex 3Gas or NH xFree radical and the H free radical that is generated by the gas that contains the H atom react it on substrate, cut off R (R ') base of removing in the title complex with the N bonding, cut off simultaneously and remove the Ta-N key, form rich tantalic TaN film.
If the carbonatoms in the above-mentioned title complex surpasses 6, the remaining many problems of carbon in film are arranged.
In the formation method of above-mentioned TaN film, import unstripped gas and NH in the vacuum chamber 3Gas or NH xFree radical, on substrate, reduce starting compound, formation contains an atomic shell of reducing compound or the adsorption film of a plurality of atomic shells, to remove with R (R ') the base part cut-out of N bonding in the title complex, import the H free radical that generates by the gas that contains the H atom then, cut off the Ta-N key of aforementioned reducing compound, and cut off and to remove residual and R (R ') the base N bonding, also can form rich tantalic TaN film.This occasion, the initial unstripped gas that imports in vacuum chamber, make it be adsorbed on the substrate after, import NH 3Gas or NH xFree radical is with adsorbed unstripped gas reaction; Perhaps import unstripped gas and NH simultaneously 3Gas or NH xFree radical makes it react on substrate, reduces starting compound on the substrate, also can form the atomic shell containing reducing compound or the adsorption film of a plurality of atomic shells.In addition, in the formation method of aforementioned TaN film, the initial unstripped gas that imports is adsorbed on the substrate it in vacuum chamber, imports the H free radical that is generated by the gas that contains the H atom then, with adsorbed unstripped gas reaction; Perhaps can import the H free radical that generates by the gas that contains the H atom at first, it is adsorbed on the substrate, import unstripped gas then,, thereafter, import NH with adsorbed H free radical reaction 3Gas or NH xFree radical or also can in vacuum chamber, import unstripped gas at first, make it be adsorbed on the substrate after, import NH simultaneously 3Gas or NHx free radical and the H free radical that is generated by the gas that contains the H atom are with adsorbed unstripped gas reaction.
As according to above-mentioned formation, can be formed on C in the resulting film, N content reduces, the Ta/N ratio of components increases, and as the useful rich tantalic low resistance TaN film of guaranteeing with the Cu distribution of the adaptation of Cu film of barrier film.
Aforementioned base materials gas is preferably selected from five (dimethylamino) tantalum (PDMAT), uncle-amyl group imino-three (dimethylformamide) tantalum (TAIMATA), five (diethylamino) tantalum (PEMAT), tert-butyl imino-three (dimethylformamide) tantalum (TBTDET), tert-butyl imino-three (ethylmethyl amide) tantalum (TBTEMT), Ta (N (CH 3) 2) 3(NCH 3CH 2) 2(DEMAT), TaX 5The gas of at least a title complex of (X: be selected from the halogen atom in chlorine, bromine, the iodine).
The preferred NH of aforementioned NHx free radical, NH 2, NH 3
The above-mentioned H atomic gas that contains is preferably and is selected from H 2, NH 3, SiH 4At least a gas.
According to the formation method of above-mentioned TaN film, can obtain the tantalum in the film and the ratio of components of nitrogen and satisfy rich tantalic low-resistance film of Ta/N 〉=2.0.
The formation method of TaN film of the present invention, its feature also are, behind above-mentioned formation method formation TaN film, in the TaN film that obtains, by using with the sputter of tantalum as the target of main constituent, make the incident of tantalum particle.Like this, can also form further richness tantalic, fully satisfy the TaN film of Ta/N 〉=2.0.
After the formation method repetition for several times with above-mentioned tantalum nitride, in the TaN film that obtains, by using with the sputter of tantalum as the target of main constituent, make the incident of tantalum particle, in addition, also can alternately repeat for several times above-mentioned formation method and, in the TaN film that obtains, by using, make tantalum particle incident operation with the sputter of tantalum as the target of main constituent.By repeating sputtering process, can improve the sticking power of the barrier film that obtains, remove impurity such as carbon elimination.Further, state on the implementation during the method, usefulness operation (for example, absorption process and reaction process) arbitrarily also can implement to make tantalum particle incident operation by using with the target of tantalum as main constituent.
DC power and RF power are preferably adjusted in above-mentioned sputter, make DC power step-down, and RF power are uprised carry out.
According to the present invention, can realize that formation has C, N content is low and Ta/N ratio of components height, and conduct is guaranteed and the effect of low-resistance TaN film that the barrier film of the adaptation of wiring film (for example, Cu wiring film) is useful.
The simple declaration of accompanying drawing
Expression is used to implement the pie graph of an example of the film deposition system of film of the present invention on [Fig. 1] pattern.
[Fig. 2] is used to illustrate the schema of the film forming technology of device of using Fig. 1.
[Fig. 3] is based on the gas precedence diagram of the schema of Fig. 2.
Expression is used to implement another routine pie graph of the film deposition system of film of the present invention on [Fig. 4] pattern.
[Fig. 5] is used to illustrate the schema of the film forming technology of device of using Fig. 4.
[Fig. 6] assembled the pattern pie graph of the compound distribution membrane formation device of the film deposition system that is used to implement film of the present invention.
[Fig. 7] represents the electricalresistivity's (μ Ω cm) of each film that embodiment 1 obtains figure respectively.
The explanation of symbol
1 film deposition system, 11 vacuum chambers
12 substrates, 13 base plate keeping devices
14 unstripped gas introgressive lines, 15 NH 3Gas or NHx free radical introgressive line
16 reactant gases introgressive lines, 17 vacuum exhausts system
18 targets, 19 voltage bringing devices
20 sputter gas introgressive lines, 121 substrate-side close binders
122 barrier films, 123 wiring film side close binders
Embodiment
According to the present invention, have C, N content is low and the Ta/N ratio of components is high low-resistance TaN film, can be by above-mentioned unstripped gas and the NH that contains the tantalum title complex that contain in vacuum chamber 3The reaction of gas, generation has Ta-N-NH on substrate xThe reducing compound of key obtains this resultant and the H free radical reaction that is generated by the compound that contains the H atom.
Unstripped gas, NH 3Gas etc., hydrogen atoms gas can be according to the such direct importings of above-mentioned gas, also can and N 2Rare gas elementes such as gas or Ar gas import together.About the amount of these reactant, NH 3Gas is with respect to unstripped gas, for example,, use with the flow about 100-1000sccm with respect to unstripped gas 5sccm, in addition, the hydrogen atoms chemical compound gas for example, with respect to unstripped gas 5sccm, with 100～1000sccm (H 2Conversion) flow uses.
The temperature of above-mentioned two reactions gets final product so long as react the temperature that takes place, for example, and unstripped gas and NH 3The reduction reaction of gas generally below 300 ℃, is preferably 150～300 ℃, and in addition, the reaction of the resultant of this reaction and H free radical generally below 300 ℃, is preferably 150～300 ℃.In such occasion, as carrying out the absorption of unstripped gas in the temperature below 20 ℃, its adsorptive capacity increases, and as its result, can improve the rate of film build of tantalum nitride.In addition, the temporary transient pressure in the vacuum chamber is preferably 1～100Pa in the occasion of the reduction reaction of beginning, is preferably 1～100Pa in the occasion of ensuing film formation reaction.
As mentioned above, title complex is the compound of coordination N=(R, R ') (alkyl of R and R ' expression carbonatoms 1-6 can be identical group separately, also can be different groups) around tantalum element (Ta).This alkyl for example can be, methyl, ethyl, propyl group, butyl, amyl group, hexyl can be straight chains, also can be side chains.This title complex is generally the compound of 4 to 5 N-of coordination (R, R ') around Ta.
The method of the invention described above for example, can make unstripped gas in vacuum chamber after absorption on the substrate, imports NH 3Gas carries out reduction reaction, generation has the reducing compound of Ta-N-NHx key, then, imports the H free radical that generates from the hydrogen atoms compound, form TaN film, then, this technology is repeated desirable several, also can be after should adsorbing and reduction reaction repeated desirable number of times, import the H free radical and form TaN film, then, this technology is repeated desirable several, perhaps also can be with unstripped gas and NH 3Gas or NHx free radical import simultaneously, after carrying out reduction reaction on the substrate, import the H free radical and form TaN film, then, this technology are repeated desirable several, perhaps make starting compound absorption in addition after, with unstripped gas and NH 3Gas or NH xFree radical and H free radical import simultaneously, and this technology is repeated desirable several, also can form TaN film.
The formation method of TaN film of the present invention so long as can implement the film deposition system of so-called ALD method, can be implemented with being not particularly limited.For example, as shown in Figure 1, so long as the device that film is formed, possess and import the unstripped gas introgressive line that contains as the unstripped gas of the tantalum of the formation element of film, import NH 3Gas or NH xThe device of the reactant gases introgressive line of the introgressive line of free radical and importing reactant gases gets final product.In addition, also can use as the film deposition system shown in Fig. 4 of its distortion.At above-mentioned NH xIn free radical introgressive line or the reactant gases introgressive line, preferably possess the free radical generating apparatus that is used to generate free radical, as free radical generation method, so-called plasma mode or catalyzer mode can.
But, in the tantalum nitride formation method of the present invention, before this barrier film forms, the known degassing that is necessary to remove the impurity such as gas that adsorb on substrate surface is handled, and has, after forming barrier film on this substrate again, at last, form the wiring film that for example contains Cu.Therefore, but if the carrying room of process vacuum exhaust, with this film deposition system so long as be connected with degas chamber and distribution film formation chamber at least, the feasible conveyance robot that utilizes can just can implement a series of operation till the formation from the pre-treatment to the wiring film with this device with substrate from the carrying room compound distribution membrane formation device that conveyance ground constitutes between film deposition system, degas chamber and distribution filming chamber.
Below, as above-mentioned film deposition system,, describe according to the schema shown in Fig. 2 and Fig. 5 for using the device shown in Fig. 1 and Fig. 4 to implement an embodiment of the occasion of method of the present invention.
In Fig. 1, below the vacuum chamber 11 of film deposition system 1, be provided with the base plate keeping device 13 of load board 12.Base plate keeping device 13 is made of the platform 131 of load board 12 and the heater 132 of the substrate 12 of lift-launch on this platform.
In vacuum chamber 11, unstripped gas introgressive line 14 is connected with introducing port (not shown) in the sidewall upper shed of this chamber, in addition, and NH 3Gas or NH xFree radical introgressive line 15 is connected with other introducing port.In Fig. 1, show that gas introgressive line 14 and 15 patterns ground vertically connect side by side on the same side, but also can laterally connect side by side, as long as can reach desirable purpose, without limits to its link position.This unstripped gas is to contain the gas that the metal that becomes the raw material of the barrier film of formation on substrate 12 constitutes the organometallic compound of element (Ta) in chemical structure.This unstripped gas introgressive line 14 is made of the gas cylinder 141 of filling unstripped gas, gas trap 142, the gas introduction tube 143 that is connected with the unstripped gas introducing port by this valve, though do not show among the figure, uses the mass flow control device can carry out dominant discharge.In addition, NH 3Gas or NH xFree radical introgressive line 15 equally also is to generate the equipment (not shown) by gas cylinder 151, gas trap 152, gas introduction tube 153, mass flow control device (not shown), free radical to be constituted.
About unstripped gas introgressive line 14, also can use above-mentioned unstripped gas filling gas cylinder, in addition, also above-mentioned organometallic compound can be accommodated in the container of heat tracing, in container, supply with by mass flow control device etc. as the rare gas elementes such as Ar of bubbled gas and to make the raw material distillation, together unstripped gas is imported in the film deposition system with bubbled gas, also can be by in the unstripped gas importing film deposition systems with gasification such as gasifier.
In addition, in vacuum chamber 11, with import unstripped gas and NH 3Gas or NH xThe introducing port (not shown) place of the position upper shed that the position of the introducing port opening of free radical is different is connected with reactant gases introgressive line 16.This reactant gases is and unstripped gas and NH 3The resultant of reaction of gas or NHx free radical reacts, the gas that the metallic film (TaN) that contains tantalum in chemical structure is separated out, for example, hydrogen, ammonia etc.This reactant gases introgressive line 16 is with unstripped gas introgressive line 14 and NH 3Gas or NH xThe occasion of free radical introgressive line 15 is same, as long as can reach desirable purpose, its link position without limits, for example, gas introgressive line 14 and 15 also can connect in same side.
The gas introduction tube 163 that this reactant gases introgressive line 16 is connected with the reactant gases introducing port by the gas cylinder 161 that is filled with reactant gases, gas trap 162, by this valve, the free radical generating apparatus 164 between gas trap 162 and reactant gases introducing port constitute, though do not show among the figure, be connected yet with the mass flow control device.Open gas trap 162, by gas introduction tube 163 supply response gas in free radical generating apparatus 164, free radical is generated from gas cylinder 161.This free radical is imported the inside of vacuum chamber 11.
But, the introducing port of unstripped gas and NH 3Gas or NH xThe relation of the position of the introducing port of free radical and the introducing port of reactant gases is in order to make unstripped gas and NH 3Gas or NH xWhen free radical reacts on the surface of substrate 12, make the reaction of the resultant that obtains and reactant gases form desirable barrier film, the introducing port of wishing any one gas is near opening base plate keeping device 13 all.Therefore, as shown in Figure 1, for example, unstripped gas, NH 3Gas or NH xThe introducing port of free radical and reactant gases can be in the side of vacuum chamber 11, at the local opening that leans on a little than the horizontal direction on the surface of substrate 12.In addition, gas introgressive line 14,15,16 also can connect into the form that separately gas is imported from the top part of wafer (wafer).
Further, in vacuum chamber 11, offer different with the introducing port of above-mentioned each gas, to be used for vacuum exhaust be the 17 venting port (not shown) that are connected.With above-mentioned raw materials gas, NH 3Gas or NH xWhen free radical and reactant gases are 17 exhausts from vacuum exhaust,, in addition,, preferably near base plate keeping device 13, offer above-mentioned venting port for exhaust is complete as far as possible in order to reduce these gases as far as possible to vacuum chamber top board direction flowing pollution wall.Therefore, as shown in Figure 1, venting port can be opened in the bottom surface of vacuum chamber 11.
Below, the Fig. 2 as schema according to an embodiment that is used to illustrate the technology of using film deposition system shown in Figure 11 to form TaN film describes.
After the pretreatment procedures such as the degassing on substrate 12 surfaces were finished, utilizing vacuum exhaust was 17, under known pressure, this substrate 12 was moved in the film deposition system 1 after the vacuum exhaust (S1).According to the occasion difference, on this substrate, known substrate close binder can be set on insulation layer.For example, can be to use common sputter gas such as Ar, on target, apply voltage plasma is produced, target is carried out sputter, on the surface of substrate, form substrate as the substrate-side close binder of metallic membrane.
The pressure of defined is preferably in vacuum exhaust to 10 -5In the following film deposition system 1 of Pa, move into aforesaid substrate 12 (S1) after, with well heater 132 this substrate is heated to the temperature of defined, for example (S2) below 300 ℃.Then, importing contains Ar, N 2After the Purge gas (S3-1) Deng rare gas element,, import the unstripped gas (MO gas) that comprises the organometallic compound that contains tantalum, on the surface of substrate, make this unstripped gas absorption (S3-2) from unstripped gas introgressive line 14 at the near surface of substrate.Then, close the gas trap 142 of unstripped gas introgressive line 14, stop to import unstripped gas, utilizing vacuum exhaust is 17 unstripped gas to be discharged (S3-3).
Then, stop Purge gas, carry out the vacuum exhaust (S3-4) of Purge gas.
After the exhaust of unstripped gas finishes, from NH 3Gas or NH xFree radical introgressive line 15 imports for example NH about 100-1000sccm in film deposition system 1 3Gas or NH xFree radical (for example, NH 3Gas) (S3-5), make itself and the unstripped gas reaction that is adsorbed on the substrate, generation has Ta-N-NH xThe compound of key (S3-6).In this occasion, if surpass 1000sccm, the resistance value of the barrier film that then obtains at last can not reach desirable value.In addition, if be lower than 100sccm, residual carbon in the film then, resistance value does not reduce.Above-mentioned reducing compound is closed NH after generating 3Gas or NH xThe gas trap 152 of free radical introgressive line 15 stops NH 3Gas or NH xThe importing of free radical, utilizing vacuum exhaust is 17 gas to be discharged (S3-7).
Continue above-mentioned vacuum exhaust, in film deposition system 1, import the free radical (S3-8) of reactant gases simultaneously by free radical generating apparatus 164 from reactant gases introgressive line 16, make the H free radical and the lip-deep above-mentioned resultant reaction specific time that is adsorbed on substrate 12 of reactant gases, make this resultant decompose (S3-9).Then, the gas trap 162 of off-response gas introgressive line 16 stops to import reactant gases, and utilizing vacuum exhaust is 17 reactant gases to be got rid of (S3-10).
Through above-mentioned operation, the extremely thin metallic film of formation atomic shell degree on aforesaid substrate side close binder from S3-1 to S3-10, that is, and barrier film (S4).
Repeat the number of times of above-mentioned operation defined from S3-1 to S3-10, reach desirable thickness (S5), form TaN film as barrier film with desirable resistance value up to this barrier film.
For the substrate that is formed with TaN film with desirable thickness, according to different occasions, for example, also can be according to known sputtering method, use sputter gas such as Ar, on target, apply voltage and make plasma generation, target is carried out sputter, surface at above-mentioned TaN film forms metallic film, promptly forms wiring film side close binder (barrier film side group bottom) (S6).
Operation through above forms stacked film on substrate 12, then, on the close binder of above-mentioned wiring film side, form wiring film.Gas according to the schema of Fig. 2 is shown in Fig. 3 in proper order.
Fig. 4 is the other film deposition system that is used to implement TaN film formation method of the present invention, is the film deposition system that further is provided with sputtering target in the device of Fig. 1, makes to carry out sputter simultaneously.With the same formation element of Fig. 1 in used same symbol, it illustrates omission.
Above vacuum chamber 11, the position on the opposite of base plate keeping device 13 is provided with target 18.On target 18, be connected with for sputter is carried out on its surface, what produce plasma body that the particle that makes the target constitute emits applies voltage device 19.In addition, target 18 is made of as the material of principal constituent the element (Ta) that constitutes with the metal that contained in the above-mentioned unstripped gas.This voltage add-on device 19 is made of volts DS generating unit 191 and the electrode 192 that is connected on the target 18.This voltage add-on device also can be an overlapping alternative device on direct current.In addition, also can be on base plate keeping device, to connect high frequency generating apparatus, form that can applying bias.
In vacuum chamber 11, with import above-mentioned raw materials gas, NH 3Gas or NH xThe introducing port (not shown) place of the position upper shed that the position of the introducing port opening of free radical and reactant gases is different is connected with sputter gas introgressive line 20.This sputter gas is so long as known rare gas element, and for example argon gas, xenon etc. just can.The mass flow control device that does not have to show among the gas introduction tube 203 that this sputter gas introgressive line 20 is connected by the gas cylinder 201 that is filled with sputter gas, gas trap 202, introducing port by this valve and sputter gas, the figure constitutes.
But, for introducing port, the NH of unstripped gas 3Gas or NH xThe position of the introducing port of free radical and the introducing port of reactant gases as described above, for the reaction of stipulating on the surface of substrate 12, forms desired barrier film, preferably near also opening base plate keeping device 13 of the introducing port of each gas.On the other hand, because the introducing port of above-mentioned sputter gas is used for the generation of sputter gas at the plasma body on sputtering target 18 surfaces, so near preferred opening target 18 of this introducing port.
In order to prevent owing to above-mentioned raw materials gas, NH 3Gas or NH xThe importing of free radical and reactant gases and pollute target 18, unstripped gas, NH 3Gas or NH xThe introducing port of free radical and reactant gases is preferably leaving the position opening of target 18.In addition, in order to stop owing to sputter gas causes above-mentioned raw materials gas, NH 3Gas or NH xFree radical and reactant gases are diffused into target 18 sides, and the introducing port of sputter gas is preferably leaving the position opening of base plate keeping device 13.Therefore, as shown in Figure 4, can be with unstripped gas, NH 3Gas or NH xThe introducing port of free radical and reactant gases the side of vacuum chamber 11, than the horizontal direction on the surface of substrate 12 a little above opening, with the introducing port of sputter gas in the side of vacuum chamber 11, than the horizontal direction on the surface of target 18 lower opening a little.
In addition, with above-mentioned raw materials gas, NH 3Gas or NH xWhen free radical and reactant gases are 17 exhausts from vacuum exhaust, flow and pollute target to target 18 directions in order not make these gases, preferred above-mentioned venting port is near base plate keeping device 13 and leave the position opening of target 18.Therefore, as shown in Figure 4, can make venting port as described above at the bottom surface of vacuum chamber 11 opening.
As described above, the film deposition system of Fig. 4 can utilize the film forming and unstripped gas, the NH of utilization on heated substrate of sputter in same vacuum chamber 11 3Gas or NH xThe film forming of free radical, reactant gases.
Fig. 5 is the schema for the embodiment that the technology when using film deposition system shown in Figure 4 to form stacked film is described.Below, be that main body describes with the place different with the schema of Fig. 2.
According to known method, after the pretreatment procedure of the degassing on the surface of substrate 12 etc. finishes, substrate 12 moved into to utilize vacuum exhaust be that 17 vacuum exhausts are in the film deposition system 1 of the pressure of regulation (S1).
After moving into substrate 12, according to the occasion difference, for example, according to known sputtering method, from sputter gas introgressive line 20 import Ar etc. sputter gas (S2), apply voltage from 19 pairs of targets 18 of voltage bringing device and make plasma generation (S3), sputtering target 18, also can form metallic film, promptly on the surface of substrate 12, substrate-side close binder (substrate-side stratum basale) (S4).
After operation S4 finishes, substrate 12 is heated to the temperature (S5) of regulation with well heater 132, then, make the operation from S6-1 to S6-10 as shown in Figure 5, implement equally with the operation of Fig. 2, on aforesaid substrate side close binder, form the quite thin metallic film of atomic shell degree, promptly as the TaN film (S7) of barrier film from operation S3-1 to S3-10.The operation (S8) of repeatable operation from above-mentioned S6-1 to S6-10 reaches the thickness of expectation up to this barrier film.Occasion based on the gas flow process of the schema of Fig. 5 and Fig. 3 is same.
In addition, in the schema of Fig. 5, do not illustrate, when forming above-mentioned barrier film, in the sticking power of strengthening barrier film and the occasion of removing impurity, also can alternately repeat the operation of several and utilize sputter gas introgressive line 20 to import sputter gas, up to the thickness that reaches expectation from above-mentioned S6-1 to S6-10.
Then, after operation from above-mentioned S6-1 to S6-10 finishes, perhaps during carrying out these operations, rare gas elementes such as importing Ar make its discharge, it is the target 18 of main constituent that sputter makes as the tantalum of unstripped gas constituent, and incident is as the tantalum particle of sputtering particle in the film that forms on substrate 12.Like this, utilize sputter, can tantalum be incided on the substrate 12 from target 18, thus can further increase tantalum in the barrier film contain rate, the tantalic TaN film of low-resistance richness that can obtain expecting.In addition, because unstripped gas is organic tantalum compound, so by utilizing above-mentioned sputter will constitute the surface that element (tantalum) incides substrate 12, promoted decomposition, make the impurity of C and N etc. be squeezed, can obtain the few low-resistance barrier film of impurity from barrier film.
This sputter is for the tantalum particle is squeezed in the TaN film, and C and N are removed in sputter, this film is carried out upgrading carry out, because not stacked tantalum film, and need be in the condition that does not form tantalum film, promptly can utilize the tantalum particle to carry out carrying out under the condition of etching.Therefore, for example need to adjust DC power and RF power, make DC power step-down, and RF power uprises.For example, by with the DC power setting below 5kW, improve RF power, for example be 400～800W, can reach the condition that does not form tantalum film.Because RF power depends on DC power, so, can adjust the upgrading degree of film by suitably adjusting DC power and RF power.In addition, sputter temperature can be common sputter temperature, for example identical with the formation temperature of TaN film temperature.
Do as described above, substrate for the barrier film that has formed thickness with expectation, according to the occasion difference, for example according to known sputtering method, from sputter gas introgressive line 20 import Ar etc. sputter gas (S9), from 19 pairs of targets 18 of voltage bringing device apply voltage make plasma generation (S10), sputtering target 18 also can form metallic film on the surface of above-mentioned barrier film, be wiring film side close binder (barrier film side group bottom) (S11).
On substrate 12, form stacked film through above operation, then, on above-mentioned wiring film side close binder, form wiring film.
In addition, as described above, pollute in order to prevent target, in above-mentioned operation, unstripped gas, NH 3Gas or NH xThe importing of free radical and reactant gases is carried out in the position of leaving target 18, further causes above-mentioned raw materials gas, NH in order to prevent owing to sputter gas 3Gas or NH xFree radical and reactant gases are diffused into target 18 sides, and the importing of sputter gas is preferably carried out in the position of leaving base plate keeping device 13.
In addition, with above-mentioned raw materials gas, NH 3Gas or NH xWhen free radical and reactant gases are 17 exhausts from vacuum exhaust, pollute target for these gases are flowed to target 18 directions, preferably near base plate keeping device 13 and the position of leaving target 18 carry out above-mentioned exhaust.
The expression of Fig. 6 pattern ground has the pie graph of the compound distribution membrane formation device of the film deposition system 1 shown in Fig. 1 and 4.
This compound distribution membrane formation device 100 comprises pre-treatment portion 101, film forming handling part 103 and the transhipment department 102 that is connected them.Each one is before handling, and making it inner in advance is vacuum.
At first, in pre-treatment portion 101, the processing prebasal plate that disposes in moving into chamber 101a utilizes pre-treatment portion side to take out of to move into the 101b of robot moves into degas chamber 101c.Heat treated prebasal plate in this degas chamber 101c makes evaporations such as the moisture processing that outgases on surface.Then, the substrate utilization that this degassing is handled is taken out of and is moved into the 101b of robot and move among the reduction treatment chamber 101d.In this reduction treatment chamber 101d, carry out following anneal, that is, the heating aforesaid substrate utilizes the reducing gas of hydrogen etc. to remove the metal oxide of sub-cloud distribution.
After anneal finishes, utilize to take out of and move into the 101b of robot, move into transhipment department 102 from reduction treatment chamber 101d taking-up aforesaid substrate.The film forming handling part side that is handed off to film forming handling part 103 by transhipment department 102 by the substrate moved into is taken out of and is moved among the 103a of robot.
Taken out of by the aforesaid substrate utilization that joined and to move into the 103a of robot and move among the 103b of filming chamber.The 103b of this filming chamber is equivalent to above-mentioned film deposition system 1.In the 103b of filming chamber, formed the stacked film of barrier film and close binder, utilized to take out of and move into the 103a of robot and take out of, moved among the 103c of wiring film chamber from the 103b of filming chamber.Here, at the top formation wiring film of above-mentioned barrier film (forming the occasion of close binder on barrier film, is close binder).Form after the wiring film, this substrate utilization is taken out of move into the 103a of robot and move to from wiring film chamber 103c and take out of chamber 103d and take out of.
As above-mentioned, adopt a succession of carry out above-mentioned stop the operation of film formed front and back, promptly, degassing process and wiring film form the formation of the above-mentioned compound distribution membrane formation device 100 of operation, can improve operating efficiency.
In addition, the formation of above-mentioned compound distribution membrane formation device 100, in pre-treatment portion 101 degas chamber 101c and each one of reduction treatment chamber 101d are set, each one of 103b of filming chamber and 103c chamber, wiring film chamber are set in film forming handling part 103, but are not limited to this formation.
In view of the above, for example, make the polygon that is shaped as of pre-treatment portion 101 and film forming handling part 103, a plurality of above-mentioned degas chamber 101c and reduction treatment chamber 101d and 103b of filming chamber and wiring film chamber 103c are set on each face, can further improve processing power.
Embodiment 1
In the present embodiment, use film deposition system 1 shown in Figure 1, as unstripped gas use five (dimethylamino) tantalum (MO) gas, as NH 3Gas or NH xFree radical uses NH 3Gas, and, form TaN film according to process flow sheet shown in Figure 2 by the H free radical that reactant gases generates.
According to known method, implementing to have SiO 2Behind the degassing pretreatment procedure on the surface of the substrate 12 of insulating film, utilizing vacuum exhaust is 17 vacuum exhausts to 10 -5In the film deposition system 1 below the Pa, move into substrate 12 (S1).As this substrate, be not particularly limited, for example also can use following substrate, that is,, use the Ar sputter gas according to common sputtering method, to having with Ta is that the target of main constituent applies voltage and makes plasma generation, and sputtering target forms the substrate of substrate-side close binder on the surface.
After in film deposition system 1, moving into substrate 12, this substrate is heated to 250 ℃ (S2) with well heater 132.Then, import the Ar Purge gas after, from unstripped gas introgressive line 14, supply with above-mentioned raw materials gas 5 seconds (S3-1, S3-2) at the near surface of substrate with 5sccm.After the surface of substrate 12 makes unstripped gas absorption, close the gas trap 142 of unstripped gas introgressive line 14, stop to import unstripped gas, utilizing vacuum exhaust is 17, exhaust is 2 seconds in film deposition system 1, discharges unstripped gas (S3-3).
Then, stop the Ar Purge gas, carry out the vacuum exhaust (S3-4) of Purge gas.
Continue vacuum exhaust on one side, on one side in film deposition system 1, from NH 3Gas or NH xFree radical introgressive line 15 imports NH with 200sccm 35 seconds (S3-5) with the unstripped gas of adsorbing (MO gas) reaction, generates the reducing compound (S3-6) with Ta-N-NHx key on substrate.Then, stop to import NH 3Gas or NH xFree radical carries out vacuum exhaust (S3-7).
Proceed above-mentioned vacuum exhaust, make H 2Gas flows to the free radical generating apparatus 164 from reactant gases introgressive line 16, the H free radical that generates is imported in the film deposition system 1 (S3-8), make the time of the lip-deep above-mentioned reduction resultant reaction defined of this free radical and substrate 12, make resultant decompose (S3-9).
After above-mentioned reaction finished, the gas trap 162 of off-response gas introgressive line 16 stopped to import reactant gases, and utilizing vacuum exhaust is 17, made film deposition system 1 interior exhaust 2 seconds, discharged reactant gases (S3-10).
To the operation of S3-10, on aforesaid substrate side close binder, form the extremely thin metallic film of atomic shell degree through the above-mentioned S3-1 that associates, that is, and as the barrier film (S4) of the tantalic tantalum nitride of richness.
Repeat the number of times of operation regulation, reach the thickness (S5) of expectation up to this barrier film from above-mentioned S3-1 to S3-10.The composition of the barrier film of Huo Deing is Ta/N=2.1 like this, and C content is below 1%, and N content is 33%.
In addition, for relatively, for using above-mentioned raw materials gas (MO gas) and NH 3The occasion of gas, and use MO gas and NH xThe occasion of free radical, and the occasion of using MO gas and H free radical are according to the aforesaid method film forming.
To the film separately that obtains with aforesaid method, calculate electricalresistivity (μ Ω cm), mapping is Fig. 7.This resistivity is to measure sheet resistance (Rs) with 4 probes probes methods, measures thickness (T) with SEM, and based on formula: ρ=RsT calculates.
As can clearly learning, use NH from Fig. 7 3After gas conversion (reduction) unstripped gas (MO gas), circulation reactant gases (H free radical) carries out film forming occasion, with use MO gas and NH 3The film forming occasion of gas (tens thousand of μ Ω cm), use MO gas and NH xFilm forming occasion of free radical (20,000 thousands of μ Ω cm) and use MO gas and the film forming occasion of H free radical (8,000 μ Ω cm) are compared, and have obtained low resistivity (430 μ Ω cm).
This thinks by MO gas and NH 3Gas or NH xThe reaction of free radical or H free radical can not fully remove R (alkyl), be C, demonstrates resistivity and does not reduce.
On the other hand, think using MO gas and NH 3In the film forming of gas and H free radical, by using NH 3Gas or NH xFree radical and H free radical show and fully to have removed R (alkyl), and C, N contain proportional reduction, and the film of formation is formed and is rich in Ta, and the resistivity of film reduces.
As described above, substrate for the barrier film of the thickness that obtains to have expectation, according to occasion, for example, according to known method, use the Ar sputter gas, target is applied voltage make plasma generation, sputtering target also can form metallic film, promptly on the surface of above-mentioned barrier film, as the wiring film side close binder (S6) of stratum basale.
Form through above operation on the substrate 12 of stacked film, form the occasion of above-mentioned barrier film side close binder, in the above, form the Cu wiring film according to known processing condition.Confirm the binding property excellence between each film.
Embodiment 2
In the present embodiment, use film deposition system 1 shown in Figure 4, use gas, the NH of five (dimethylamino) tantalum (MO) as unstripped gas 3Gas and as reactant gases uses the gas that produces the H free radical, forms TaN film according to process flow sheet shown in Figure 5.
Operation similarly to Example 1, the substrate 12 that will carry out surperficial degassing pretreatment procedure is moved into and utilized vacuum exhaust is 17 vacuum exhausts to 10 -5The film deposition system 1 interior (S1) that Pa is following.
After moving into substrate 12, according to occasion, for example, from sputter gas introgressive line 20 import Ar (S2) as sputter gas, the target 18 that contains Ta from 19 pairs of voltage bringing devices applies voltage makes plasma generation (S3), sputtering target 18, also can form metallic film, promptly, substrate-side close binder (S4) on the surface of substrate 12.
After operation S4 finishes,, after the circulation Ar Purge gas,, supply with above-mentioned raw materials gas 5 seconds with 5sccm from unstripped gas introgressive line 14 at the near surface of substrate with well heater 132 12 to 250 ℃ of heated substrates (S5).
Same to S3-10 with embodiment 1 from operation S3-1, implement shown in Fig. 5 from operation S6-1 to S6-10, on aforesaid substrate side close binder, separate out the extremely thin metallic film of atomic shell degree, form as the barrier film (S7) that is rich in the TaN film of Ta.
Carry out the number of times of operation regulation repeatedly, reach up to this barrier film (S8) till the thickness of expectation from above-mentioned S6-1 to S6-10.In the tantalum nitride that obtains like this, the occasion of the content of Ta/N ratio of components, C and N and the resistivity of resulting film and embodiment 1 is same.
In addition, when forming above-mentioned barrier film,, also can alternately repeat the operation of several and utilize sputter gas introgressive line 20 to import sputter gas, up to the thickness that reaches expectation from above-mentioned S6-1 to S6-10 in the sticking power of strengthening barrier film and the occasion of removing impurity.
Then, after the operation from above-mentioned S6-1 to S6-10 finishes, perhaps during carrying out these operations, import Ar and make its discharge, sputter is the target 18 of main constituent with tantalum, and incident is as the tantalum particle of sputtering particle in the film that forms on substrate 12.This sputtering condition is DC power: 5kW, RF power: 600W.Sputter temperature is carried out at 250 ℃ in addition.
By squeezing into the sputter of above-mentioned tantalum particle, what can further increase tantalum in the barrier film contains rate, the tantalic TaN film of low-resistance richness that can obtain expecting.By tantalum being incided the surface of substrate 12, promoted decomposition in addition, the impurity of O or C or N etc. is squeezed from barrier film, can obtain the few low-resistance barrier film of impurity.The film that obtains like this is Ta/N=3.5, C content: below 0.1%, N content: 22% and the resistivity of the film that obtains be: 90 μ Ω cm.
After operation forms the upgrading TaN film of the thickness of expecting as described above, according to occasion, for example, according to known method, import Ar sputter gas (S9), apply voltage from 19 pairs of targets 18 of voltage bringing device and make plasma generation (S10), sputtering target 18 from sputter gas introgressive line 20, also can form metallic film on the surface of above-mentioned barrier film, that is, and as the wiring film side close binder (S11) of stratum basale.
Having formed on the substrate 12 of stacked film through above operation, form the occasion of above-mentioned wiring film side close binder, form the Cu wiring film according to known processing condition thereon.Confirm the binding property excellence between each film.
In addition, such as described above, pollute in order to prevent target, in above-mentioned operation, import unstripped gas, NH 3Gas or NH xFree radical, reactant gases carry out in the position of leaving target 18, and further in order to stop owing to sputter gas causes these gaseous diffusion to target 18 sides, the importing of therefore preferred sputter gas is carried out in the position of leaving base plate keeping device 13.
In addition, be 17 discharge above-mentioned raw materials gases, NH from vacuum exhaust 3Gas or NH xWhen free radical, reactant gases, for do not make these gases to target 18 directions flow and pollute target preferably near base plate keeping device 13 and the position of leaving target carry out above-mentioned exhaust.
Embodiment 3
As unstripped gas, substitute five (dimethylamino) tantalum, use uncle-amyl group imino-three (dimethylamino) tantalum, when being implemented as membrane process according to embodiment 1 in addition, obtain being rich in low-resistance TaN film of Ta.For the film that obtains, be Ta/N=1.95, C content: N content 1.0%: 34%, resistivity is 400 μ Ω cm.
Utilizability on the industry
According to the present invention, can form, Ta/N low as C, N content form than high, guarantee the low-resistance TaN film useful with the barrier film of the adaptation of Cu film. Therefore, the present invention can be applicable in the film forming technology of field of semiconductor devices.

Claims (19)

1. the formation method of TaN film is characterized in that, in vacuum chamber, importing has contained in the coordination on every side of tantalum atom unstripped gas, the NH of the title complex of N=(R, R ') 3Gas or NH xFree radical and the H free radical that generates by the gas that contains the H atom, it is reacted on substrate, with in the title complex with the R of N bonding, R ' base cuts off and removes, simultaneously, cut off the Ta-N key, form rich tantalic TaN film, the alkyl of R and R ' expression carbonatoms 1-6 wherein, can be identical group separately, also can be different groups, aforementioned base materials gas be from five (dimethylamino) tantalum, uncle-amyl group imino-three (dimethylformamide) tantalum, five (diethylamino) tantalum, tert-butyl imino-three (dimethylformamide) tantalum, gas with at least a title complex of selecting in tert-butyl imino-three (ethylmethyl amide) tantalum.
2. the formation method of the TaN film of claim 1 record is characterized in that, imports aforementioned base materials gas and NH in aforementioned vacuum chamber 3Gas or NH xFree radical, on substrate, reduce starting compound, formation contains an atomic shell of reducing compound or the surface adsorption film of several atomic shells, part is cut off and to be removed in the title complex and R, R ' base the N bonding, import the H free radical that generates by the gas that contains the H atom then, cut off the Ta-N key of aforementioned reducing compound, and cut off and to remove residual and R, R ' base the N bonding, form rich tantalic TaN film.
3. the formation method of the TaN film of claim 2 record is characterized in that, the initial aforementioned base materials gas that imports in aforementioned vacuum chamber, make it be adsorbed on the substrate after, import aforementioned NH 3Gas or NH xFree radical with adsorbed unstripped gas reaction, perhaps imports aforementioned base materials gas and NH simultaneously 3Gas or NH xFree radical reacts it on substrate, reduce starting compound on substrate, forms to contain an atomic shell of reducing compound or the surface adsorption film of a plurality of atomic shells.
4. the formation method of the TaN film of claim 1 record, it is characterized in that the initial aforementioned base materials gas that imports is adsorbed on the substrate it in aforementioned vacuum chamber, import the aforementioned H free radical that generates by the gas that contains the H atom then, itself and adsorbed unstripped gas are reacted, and the perhaps initial H free radical that imports aforementioned by the gas generation that contains the H atom is adsorbed on the substrate it, import aforementioned base materials gas then, with adsorbed H free radical reaction, thereafter, import aforementioned NH 3Gas or NH xFree radical.
5. the formation method of the TaN film of claim 1 record is characterized in that, the initial aforementioned base materials gas that imports in aforementioned vacuum chamber, make it be adsorbed on the substrate after, import aforementioned NH simultaneously 3Gas or NH xFree radical and the H free radical that is generated by the gas that contains the H atom react itself and adsorbed unstripped gas.
6. the formation method of the TaN film of each record of claim 1～5 is characterized in that, aforementioned NH xFree radical is NH, NH 2, NH 3Free radical.
7. the formation method of the TaN film of each record of claim 1～5 is characterized in that, the gas of the aforementioned H of containing atom is to be selected from H 2, NH 3, SiH 4At least a gas.
8. the formation method of TaN film, it is characterized in that, after the formation method of each record by claim 1～7 forms TaN film, in the TaN film that obtains, by using, make the incident of tantalum particle with the sputter of tantalum as the target of main constituent.
9. the formation method of TaN film is characterized in that, after the formation method of each record by repeating for several times claim 1～7, by using with the sputter of tantalum as the target of main constituent, the tantalum particle is incided in the TaN film that obtains.
10. the formation method of TaN film is characterized in that, alternately repeats for several times
The formation method of each record of claim 1～7 and
Make the tantalum particle incide operation in the TaN film that obtains by using as the sputter of the target of main constituent with tantalum.
11. the formation method of TaN film is characterized in that, during the formation method of each record of implementing claim 1～7, by using with the sputter of tantalum as the target of main constituent, implements to make tantalum particle incident operation.
12. the formation method of TaN film is characterized in that, the initial TaX that imports in vacuum chamber 5Unstripped gas, wherein X is a halogen atom, and it is adsorbed on the substrate, imports NH then simultaneously 3Gas or NH xFree radical and the H free radical that is generated by the gas that contains the H atom react itself and adsorbed unstripped gas.
13. the formation method of TaN film is characterized in that, the initial TaX that imports in vacuum chamber 5Unstripped gas, wherein X is a halogen atom, it is adsorbed on the substrate, imports the aforementioned H free radical that generates by the gas that contains the H atom then, itself and adsorbed unstripped gas are reacted, the perhaps initial H free radical that imports aforementioned by the gas generation that contains the H atom, it is adsorbed on the substrate, imports aforementioned base materials gas then, with adsorbed H free radical reaction, import NH thereafter, 3Gas or NH xFree radical.
14. the formation method of the TaN film of claim 12 or 13 records is characterized in that aforementioned NH xFree radical is NH, NH 2, NH 3Free radical.
15. the formation method of the TaN film of claim 12 or 13 records is characterized in that the gas of the aforementioned H of containing atom is to be selected from H 2, NH 3, SiH 4At least a gas.
16. the formation method of TaN film, it is characterized in that, after the formation method of each record by claim 12～15 forms TaN film, in the TaN film that obtains, by using, make the incident of tantalum particle with the sputter of tantalum as the target of main constituent.
17. the formation method of TaN film is characterized in that, after the formation method of each record by repeating for several times claim 12～15, by using with the sputter of tantalum as the target of main constituent, the tantalum particle is incided in the TaN film that obtains.
18. the formation method of TaN film is characterized in that, alternately repeats for several times
The formation method of each record of claim 12～15 and
Make the tantalum particle incide operation in the TaN film that obtains by using as the sputter of the target of main constituent with tantalum.
19. the formation method of TaN film is characterized in that, during the formation method of each record of implementing claim 12～15, by using with the sputter of tantalum as the target of main constituent, implements to make tantalum particle incident operation.
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